Process for the treatment of an aqueous mixture comprising a dipolar aprotic compound

ABSTRACT

Processes for the treatment of an aqueous mixture comprising a dipolar aprotic compound, comprise:
         a) an adsorption step, in which the aqueous mixture is brought into contact with a porous adsorbent, whereby the porous adsorbent is chosen such that the dipolar aprotic compound adsorbs to it more readily than water;   b) a desorption step, in which the porous adsorbent is brought into contact with a desorbing agent, whereby a recovery solution is formed comprising the desorbing agent and the dipolar aprotic compound.

This application is a divisional of commonly owned U.S. application Ser.No. 12/097,653, filed 31 Oct. 2008 (now U.S. Pat. No. 8,183,389), whichis the national phase application under 35 USC §371 ofPCT/EP2006/012331, filed 20 Dec. 2006 which designated the U.S. andclaims benefit of EP 05027936.3, filed 20 Dec. 2005, the entire contentsof each of which are hereby incorporated by reference.

The invention relates to a process for the treatment of an aqueousmixture comprising a dipolar aprotic compound, for the purpose ofremoving the dipolar aprotic compound from the aqueous mixture andpreferably the subsequent retrieval of it.

Such a process is known from DE 3834904 A1. In DE 3834904 A1, a processis disclosed for the recovery of N-methyl-2-pyrrolidone (a synonym1-methyl-2-pyrrolidone, NMP), a dipolar aprotic compound, from anaqueous solution by means of extraction with certain derivatives ofphenol such as nonylphenol.

The known extraction process has as disadvantage that the solvents asindicated are undesirable from viewpoint of toxicity and environmentalprotection.

It is the objective of the present invention to reduce or even eliminatethe said disadvantages.

The said objective is achieved in that the process comprises

-   a) an adsorption step, in which the aqueous mixture is brought into    contact with a porous adsorbent, whereby the porous adsorbent is    chosen such that the dipolar aprotic compound adsorbs to it more    readily than water;-   b) a desorption step, in which the porous adsorbent is brought into    contact with a desorbing agent, whereby a recovery solution is    formed comprising the desorbing agent and the dipolar aprotic    compound.

The advantage of the process according to the invention is that it isnot necessary to rely on an extraction step and the associated need forspecifically chosen extraction compounds to achieve the retrieval of thedipolar aprotic compound. Nevertheless, the process according to theinvention can result in the dipolar aprotic compound being retrieved inhigh percentages, even close to 100%. An additional advantage of theprocess according to the invention is that a purified aqueous mixture isobtained without residues of extraction agents as in the known process.

The process according to the invention relates to the treatment of anaqueous mixture comprising a dipolar aprotic compound. In the aqueousmixture, which is typically in liquid form, water is a continuous phase;other compounds may also be present, although it is preferred that theamount of compounds that can act as desorbing agent—as discussed in moredetail below—is at most 30 wt. %, based on the aqueous mixture as awhole; more preferably this amount is at most 20 or 10 wt. %; mostpreferably, the amount in the aqueous mixture of compounds that can actas desorbing agent is essentially zero. Examples of other compounds thatmay be present in the aqueous mixture are electrolytes such as organicor inorganic salts.

The aqueous mixture to be treated in the process according to theinvention comprises a dipolar aprotic compound. Such compounds are assuch known and are generally recognised to be compounds with acomparatively high dielectric constant, typically greater than about 15,and a sizable permanent dipole moment, that cannot donate suitablylabile hydrogen atoms to form strong hydrogen bonds and thus areessentially non-protogenic. Examples of dipolar aprotic compounds thatmay advantageously be removed from an aqueous mixture in the processaccording to the invention include the group consisting ofhexamethylphosphorous triamide (HMPT), dimethylsulfoxide (DMSO),1-methyl-2-pyrrolidone (NMP), 1-ethyl-2-pyrrolidone (NEP), and ureaderivatives of the following formula (I):

wherein R₁, R₂, R₃ and R₄ may each independently be H or a C₁-C₄ alkylgroup and whereby R₂ and R₃ may be a part of a heterocyclic group. Informula (I), it is preferred that R₁, R₂, R₃ and R₄ are eachindependently H or a methyl or an ethyl group. In another embodiment, itis preferred that R₁, R₂, R₃ and R₄ are identical. In another class ofpreferred embodiments of the compound according to formula (I), R₂ andR₃ are such that compound (I) comprises a heterocyclic ring. As isknown, the term heterocyclic ring indicates a ring structure wherein thering-forming atoms are not all carbon. Since R₂ and R₃ will in the caseof ring-forming only contribute carbon atoms as ring-forming atoms, thisimplies that within the context of the present invention the twonitrogen atoms are comprised within the ring structure. If the compoundaccording to formula (I) has a heterocyclic ring, then this ring ispreferably a 5- or 6-ring. Preferred examples of compounds according toformula (I) are urea, 1,3-dimethyltetrahydro-2(1H)-pyrimidinone (DMPU)or 1,1,3,3-tetramethylurea (TMU).

The aqueous mixture may contain one dipolar aprotic compound; howeverthe process according to the invention is also applicable in case theaqueous mixture contains several dipolar aprotic compounds as identifiedabove.

The amount of the dipolar aprotic compound in the aqueous mixture mayvary within wide limits—as it indeed does in practice. It was found thatthe benefits of the process according to the invention are particularlyvisible in cases where the aqueous mixture contains relatively lowamounts of the dipolar aprotic compound. In a preferred embodiment,therefore, the aqueous mixture to be treated in the process according tothe invention contains at most 40 wt. %, more preferably at most 30, 20,10 or even at most 8, 6, 5 or even 4 wt. % of dipolar aprotic compoundor compounds, based on the total of the aqueous mixture. Surprisingly,the objectives according to the invention are even achieved when aqueousmixtures are treated that comprise at most 2 or 1 wt. % of dipolaraprotic compound or compounds, or even at most 0.5 or 0.1 wt. %.

The process according to the invention comprises an adsorption step. Inthe adsorption step, the aqueous mixture is brought into contact with aporous adsorbent. A wide variety of porous adsorbents are suitable foruse in the process according to the invention, provided that a dipolaraprotic compound adheres to it more readily than water so as to ensurethat a reduction or even removal of the dipolar aprotic compound fromthe aqueous mixture can indeed take place. Whether or not a porousadsorbent fulfils this criterion—i.e. that a dipolar aprotic compoundhas a higher affinity to it that water—may be easily tested by theskilled person through simple routine tests that are as such known. Onesuch a test comprises the following steps: in a vessel, a composition ismade containing a known concentration of a dipolar aprotic compound in aliquid aqueous system. Subsequently, a known quantity of a porousadsorbent is added to the vessel, into the composition. The compositionplus adsorbent are then stirred for about one hour. Then, a sample ofthe composition is taken, and the concentration of the dipolar aproticcompound determined. If the said concentration has decreased, then thisis an indicator that the porous adsorbent fulfils the abovementionedcriterion. Another test for determining whether a porous adsorbent issuitable for use in the process according to the invention comprises thefollowing steps: a column is filled with the porous adsorbent. A liquidcomposition—containing a known concentration of a dipolar aproticcompound in a liquid aqueous system—is fed to the top of the column andmade to flow through the porous adsorbent. As soon as the compositionexits at the bottom of the column, a sample is taken and theconcentration of the dipolar aprotic compound determined. If the saidconcentration has decreased, then this is an indicator that the porousadsorbent fulfils the abovementioned criterion.

Various types of porous adsorbents may be used in the process accordingto the invention; examples of such types are carbonaceous adsorbentssuch as activated carbon as well as resin-based adsorbents or adsorbentscomprising silica or alumina. Suitable adsorbents may comprisemicropores (herein defined as pores having an average diameter of atmost 2 nm), mesopores (herein defined as pores having an averagediameter lying between 2 and 50 nm), or macropores (herein defined aspores having an average diameter larger than 50 nm), or mixturesthereof. Preferably, the porous adsorbent comprises a mixture ofmicropores, mesopores and macropores; this has the advantage that a highadsorbing capacity of the adsorbent is combined with a goodaccessibility of the porous adsorbent for the aqueous mixture.Preferably, resin-based adsorbents are used. As is known, resin-basedporous adsorbents are obtainable in non-functionalised form or infunctionalised ion-exchange form. For the process according to theinvention, preferably porous adsorbents essentially prepared fromnon-functionalised resins are used. It is advantageous when the saidnon-functionalised resin has a high specific surface area, of preferablyat least 400, 500, 600, 700 or even 800 square meters per gram ofadsorbent (m²/g), and is cross-linked. An example of a resin suitablefor preparation of the porous adsorbent is a polystyrene-divinylbenzeneresin. Such resins and porous adsorbents made therefrom are as suchknown. Examples of a suitable porous adsorbent based on a cross-linkedpolystyrene-divinylbenzene resin are Lewatit® VP OC 1163 (Supplier:Lanxess), Amberlite® XAD 4 (supplier: Rohm & Haas), Dowex Optipore® L493(supplier: Dow Chemical) and Sepabeads® SP700 (supplier: MitsubishiChemical Corporation). As indicated, the specific surface area of theporous adsorbent is preferably at least 400, 500, 600, 700 or 800 m²/g;more preferably, the specific surface area is at least 900, 1000, 1100,1200 or even 1300 m²/g. Although there is according the invention noreason to limit the specific surface area of the porous adsorbent otherthan that there should remain a physical possibility for the dipolaraprotic compound to actually reach the majority or even entirety of thesaid surface area, it may for economic reasons be useful to choose theporous adsorbent such that the specific surface area is at most 2500 or2000 m²/g.

The bringing into contact of the aqueous mixture with the porousadsorbent may be achieved by methods as such known to the skilledperson. An example of such a method is the filling of a column with theporous adsorbent, followed by feeding the aqueous mixture to the columnand forcing the mixture to flow through it. In this case, the porousadsorbent is preferably static or even fixed and the aqueous mixture isin movement.

As is known, it takes some time for an adsorption process to reach fullequilibrium. Although waiting for full equilibrium may not alwaysrepresent the most economical fashion for carrying out the processaccording the invention, it is still preferred that the adsorption stepis carried out in such a fashion that a certain average contact timebetween porous adsorbent and aqueous mixture is achieved. Although thesaid contact time may vary within wide limits, it is preferred that itis at least 0.1 minute, so as to ensure that some adsorbing has takenplace; preferably, the said average contact time is at least 0.5, 1, 2,3, or even 5 minutes. For economical reasons, it is preferred to limitthe average contact time to at most 150 minutes, preferably 140, 130,120, 110 or 100 minutes.

The temperature and pressure at which the adsorption step are carriedout may vary within wide limits, and are primarily dependent on choosingfavourable conditions for carrying out the step in the most economicalfashion. It will often not be necessary to operate at pressures otherthan atmospheric, although this is certainly possible. Likewise,temperatures other than room temperature are often not needed butcertainly possible. It is noted hereby that an increase intemperature—e.g., from room temperature to 50° C.—is typicallyassociated with a notable decrease in the amount of dipolar aproticcompound as adsorbed by the porous adsorbent.

Subsequent to the adsorption step a), the process according to theinvention comprises a desorption step b). In the desorption step, theporous adsorbent is brought into contact with a desorbing agent. Thisimplies that it should be ensured that the porous adsorbent is thenessentially no longer in contact with the aqueous mixture; this may bedone during the desorption step—e.g. by the act of bringing thedesorbing agent in contact with the porous adsorbent—or prior to it. Thepurpose of the desorbing step is that the dipolar aprotic compound atleast partly desorbs from the porous adsorbent and dissolves in or mixeswith the desorbing agent.

As desorbing agent, any liquid is in principle suitable that, whenbrought into contact with the porous adsorbent, shows a lowerequilibrium adsorption concentration of the dipolar aprotic compound ascompared to that of the aqueous mixture. This lower equilibriumconcentration provides the driving force for the desorbing activity. Aswill immediately be evident to the skilled person, the simple tests asdescribed above for selecting a suitable porous adsorbent may also beused for determining whether a liquid is suitable as desorbing agent.Examples of compounds that may be comprised in the desorbing agent are:C₁-C₄ alkyl alcohols such as methanol and ethanol; C₃-C₄ iso-alkylalcohols such as 2-propanol; ketones such as acetone; esters such asethyl acetate; and water. The desorbing agent may also comprise amixture of the said compounds. If the desorbing agent comprises or evenconsists essentially of water, then the water preferably has atemperature that is between 10° C. and 100° C. higher, more preferablybetween 20° C. and 70° C. higher than the temperature at which theadsorption step was carried out; it is possible to use water in the formof steam. In a preferred embodiment of the desorption step according tothe invention, the desorbing agent comprises or even consistsessentially of methanol.

During the execution of desorption step b), the desorbing agent has theeffect that at least part of the dipolar aprotic compound as adsorbed tothe porous adsorbent transfers into the desorbing agent, so that a newsolution is being formed which is referred to herein as a recoverysolution. The recovery solution comprises the desorbing agent and thedipolar aprotic compound. Furthermore, the recovery solution maycomprise other compounds such as the compounds that were present in theaqueous mixture. The recovery solution may be separated from the porousadsorbent by simple means; an example thereof, in case the processaccording to the invention is carried out in such a way that the porousadsorbent and the desorbing agent have been brought together in avessel, is the draining of the said vessel after completion of thedesorption step. If the process according to the invention is carriedout using a column filled with the porous adsorbent, the recoverysolution may be collected at the outlet of the column Preferably,however, use is made of the regeneration step as disclosed below forthis purpose.

In a preferred embodiment of the process according to the invention, areplacement step a1) is executed after adsorption step a) and prior todesorption step b). In replacement step a1), the porous adsorbent isbrought into contact with a replacement solution. The said replacementsolution is preferably an aqueous solution containing less than 5 wt. %,preferably less than 2 wt. % of electrolytes based on the total weightof the replacement solution; furthermore, it is preferred that thereplacement solution contains less than 20 wt. %, more preferably lessthan 10 wt. % or 5 wt. % of a compound or compounds that can act asdesorbing agent.

Replacement step a1) is of interest in amongst others the case that theaqueous mixture contains compounds that do not dissolve in the desorbingagent. In such a case, the execution of the desorption step b) directlyfollowing adsorption step a) could lead to an accumulation ofprecipitated solid material in the porous adsorbent, which isundesirable. This issue may in certain circumstances be solved by simplyseparating the porous adsorbent from the aqueous mixture, e.g. bydraining an adsorbent-containing column if the process according to theinvention is carried out in such a way, followed by the desorption step.However, such a separating step could lead to the introduction of largevolumes of gases such as air into the system wherein the processaccording to the invention is being carried out, which is oftenundesirable. For this reason, the execution of the said separation stepis less preferred than the execution of the replacement step. As theskilled person will appreciate, the need to execute replacement step a1)depends on the specific nature of the compounds in the aqueous mixtureand on the nature of the desorbing agent. If, for example, the desorbingagent comprises or even consists essentially of an alcohol such asmethanol, then typical compounds that do not dissolve therein and thuscould prompt the need for a separation step or more preferably areplacement step comprise various salts.

Since it is preferred for practical reasons that the replacementsolution is miscible with the aqueous mixture, it is preferred that thereplacement solution is an aqueous solution. In order to avoid theabovementioned precipitation problems during desorption step b), it ispreferred that the replacement solution has a purity (related to water)in excess of 80 wt. %, preferably in excess of 90, 95 or even 99%, andcontains less than 5 wt. %, preferably less than 2 wt. % of compoundsthat have a low solubility in the desorbing agent. Low solubility isdefined herein as a solubility below 10 wt. % at room temperature.

In a preferred embodiment of the process according to the invention, aregeneration step c) is executed after desorption step b). The purposeof regeneration step c) is to bring the porous adsorbent in such acondition that the adsorption step a) can be executed in a betterfashion—i.e. a quicker and/or a higher adsorption of the dipolar aproticcompound to the porous adsorbent—compared to when the regeneration stepc) would not have been executed. In order to achieve this purpose, theporous adsorbent is brought into contact with a regeneration solution.The said regeneration solution is an aqueous solution containing lessthan 5 wt. %, preferably less than 2 wt. % of electrolytes based on thetotal weight of the regeneration solution; furthermore, it is preferredthat the regeneration solution contains less than 20 wt. %, morepreferably less than 10 wt. % or 5 wt. % of a compound or compounds thatcan act as desorbing agent. By bringing the porous adsorbent intocontact with the regeneration solution, the recovery solution will atleast be partly separated from the porous adsorbent. This is beneficialsince this separation enables the isolation of the dipolar aproticcompound from the recovery solution.

In a further preferred embodiment of the process according to theinvention, the desorption step b) or the regeneration step c) isfollowed by a recovery step d). In this recovery step d), the dipolaraprotic compound is isolated from the recovery solution. The saidisolation may be achieved by methods that are as such known to theskilled person. Examples of such methods are rectification/distillationand/or thin-film evaporation. Since the concentration of the dipolaraprotic compound in the recovery solution will typically be much higherthan in the said concentration in the aqueous mixture, the namedtechnologies now have a much higher economical feasibility. It isadvantageous to choose a desorbing agent which can be separated easilyfrom the dipolar aprotic compound using the named technologies, e.g. bychoosing a desorbing agent that either boils off very easily or has ahigher boiling point than the dipolar aprotic compound.

In many cases, the practical implementation of the process according tothe invention will involve the presence of a porous adsorbent in somesort of container, e.g. a stirred vessel or a column. In such cases, itwill be possible to determine a Bed Volume (BV). BV is then defined asthat part of the volume of the said container wherein the porousadsorbent resides. As is commonly done in processes for the treatment ofaqueous mixtures, the amounts of the various streams as used—the aqueousmixture itself but also the desorbing agent and if applicable also thereplacement solution and the regeneration solution—may be expressed inBV's, as such or per unit of time.

The number of BV's of aqueous solution that may be brought into contactwith the porous adsorbent during the adsorption step before theadsorbent has reached its maximum capacity is, as the skilled personwould expect, dependent on the initial concentration of the dipolaraprotic compound in the aqueous mixture and the adsorbing capacity ofthe porous adsorbent; the said number of BV's can be easily calculatedfrom these two input data. If exceeding of the maximum adsorptioncapacity is to be avoided, e.g. in case of working with a column andwhen the presence of the dipolar aprotic compound at the exit of thecolumn is undesirable, then the number of BV's of the aqueous mixturethat is brought into contact with the porous adsorbent should remainbelow the maximum.

The number of BV's of desorbent is preferably chosen so that theconcentration of dipolar aprotic compound in the recovery solution is ashigh as possible. This will often be the case by using between 0.5 and2.0 BV's of desorbing agent, preferably between 0.75 and 1.5 BV's, mostpreferably between 0.8 and 1.2 BV's.

The number of BV's of replacement solution and regeneration solution ispreferably as low as possible—while still being enough to fulfil inessence the objectives of the said solutions. This has the advantagethat the concentration of valuable compounds in these solutions will beas high as possible so that a recovery of the said compounds is asefficient as possible. In preferred embodiments, the number of BV's asused of the replacement solution and the regeneration solution liesbetween 0.5 and 3.

An example in industry of an aqueous mixture suitable to be treated inthe process according to the invention is a mixture that can be formedduring the synthesis of2-methyl-4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-2-butenal, aC₁₄-aldehyde that is a valuable product in itself and furthermore animportant intermediate in the synthesis of various products such asVitamin A. The C₁₄-aldehyde may be prepared from â-ionone via an as suchknown Darzens-type of condensation as disclosed in a.o. U.S. Pat. No.2,987,550. During this condensation process, it is advantageous to use adiluent, whereby it is surprisingly beneficial to use as a diluent adipolar aprotic compound like DMSO, DMPU, TMU, or NMP. Furthermore, itis advantageous to use sodium methylate and the methyl ester ofchloroacetic acid as reactants, as this leads to the formation ofmethanol as side-product, said methanol being a suitable desorbingagent. Subsequent to the condensation, a saponification step andhydrolysis step are carried out; this leads to a mixture being formedcomprising a.o. the original diluent (e.g. DMSO, DMPU, TMU, or NMP),methanol and the C₁₄-aldehyde. The C₁₄-aldehyde may be removed from themixture by means of an extraction step, whereby the extraction agent maybe for example hexane. This then leads to the formation of a wastestream; the waste stream is an aqueous mixture comprising—besideswater—methanol, the diluent and furthermore salts as formed during theprevious steps, such as inorganic salts like NaCl and NaHCO₃ and organicsalts such as CH₃OCH₂COONa and/or CH₃COONa. The methanol can be isolatedfrom the waste stream via rectification. It is then of high economic andecologic interest to remove the diluent from this waste stream and torecover it; as the diluent is a dipolar aprotic compound, this may beachieved efficiently through the process of the invention, whereby thereis an additional benefit of the potential to use methanol that wasformed as desorbing agent, thereby limiting the number of compounds usedin executing the synthesis of the C₁₄-aldehyde.

Another example of the use in industry of the process according to theinvention is the treatment of aqueous mixtures that are formed forremoving post-etch residues in the production of semiconductors; theforming of such aqueous mixtures containing a dipolar aprotic compoundlike NMP is disclosed in for example WO 2005/098920.

Yet a further example of the use in industry of the process according tothe invention is the treatment of aqueous mixtures that are formed for,or during the stripping of paint. Also those mixtures commonly containone or more dipolar aprotic compound which may be advantageously removedand preferably even recovered according to the invention.

The process according to the invention will be illustrated by means ofthe following Examples, without being limited thereto.

EXAMPLE 1

In order to assess whether Amberlite® XAD 4 (supplier: Rohm & Haas; thisadsorbent comprises a matrix of a cross-linkedpolystyrene-divinylbenzene; the adsorbent is not further functionalised)is a suitable porous adsorbent, the following experiment was done. Theadsorbent was rinsed thoroughly with deionised water. Then, 10 ml of theadsorbent was taken and put into 50 ml of a mixture of water and 4 wt. %of 1,1,3,3-tetramethylurea (TMU), under magnetic stirring. During thisadsorption step, the temperature was kept at 25° C. After one hour undercontinued magnetic stirring, the amount of TMU in the water mixture wasdetermined by means of gas chromatography (GC). The reduction of TMUconcentration in the mixture allowed the determination of the amount ofTMU that was adsorbed to the adsorbent, which was determined at 80 gramsper liter of adsorbent.

EXAMPLE 2

Example 1 was repeated, with however the difference that the dipolaraprotic compound was 1-ethyl-2-pyrrolidone (NEP), initially present inthe water in an amount of 3 wt. %. The amount of NEP as adsorbed by theadsorbent was determined at 57 grams per liter of adsorbent.

EXAMPLE 3

Example 2 was repeated, with however the difference that the porousadsorbent was Lewatit® VP OC 1064 (Supplier: Lanxess) and that NEP wasinitially present in the water in an amount of 2 wt. %. The amount ofNEP as adsorbed by the adsorbent was determined at 42 grams per liter ofadsorbent.

EXAMPLE 4

Example 1 was repeated, with however the difference that the porousadsorbent was Lewatit® VP OC 1163 (Supplier: Lanxess) and that thedipolar aprotic compound was 1,3-dimethyltetrahydro-2(1H)-pyrimidinone(DMPU), initially present in the water in an amount of 3 wt. %. Theamount of DMPU as adsorbed by the adsorbent was determined at 170 gramsper liter of adsorbent.

EXAMPLE 5

Example 1 was repeated, with however the difference that the dipolaraprotic compound was 1-methyl-2-pyrrolidone (NMP). The amount of NMP asadsorbed by the adsorbent was determined at 80 grams per liter ofadsorbent.

EXAMPLE 6

Example 5 was repeated, with however the difference that the porousadsorbent was Dowex Optipore® L493 (supplier: Dow Chemical). The amountof NMP as adsorbed by the adsorbent was determined at 85 grams per literof adsorbent.

EXAMPLE 7

Example 1 was repeated, with however the difference that the porousadsorbent was Lewatit® VP OC 1163 and the dipolar aprotic compound wasNMP. The amount of NMP as adsorbed by the adsorbent was determined at130 grams per liter of adsorbent.

EXAMPLE 8

In order to assess whether methanol is a suitable desorbing agent, theporous adsorbent Lewatit® VP OC 1163 was—after being thoroughly rinsedwith deionised water—brought into contact with a methanol mixtureconsisting of 96 wt. % methanol and 4 wt. % NMP under magnetic stirring.After one hour under continued magnetic stiffing at 25° C., the amountof NMP in the methanol mixture was determined by means of gaschromatography (GC). The reduction of NMP concentration in the mixtureallowed the determination of the amount of NMP that was adsorbed to theadsorbent, which was determined at 35 grams per liter of adsorbent.Since this amount is much lower than the equilibrium adsorptionconcentration of NMP in an aqueous system—see Example 1—it was therebyestablished that methanol can indeed serve as desorbing agent.

EXAMPLE 9

In order to execute adsorption step a) in combination with replacementstep a1), desorption step b) with methanol as desorbing agent, andregeneration step c), the following laboratory-scale work was done.

A double-walled temperature-controlled chromatography-type glass columnwas filled with porous adsorbent Lewatit VP OC 1163; the adsorbent waskept as a fixed-bed. The column was about 450 mm long with an innerdiameter of 26 mm; the bed volume (BV) was 0.178 liter adsorbent. Thecolumn was placed vertically; all liquids flowed from top to bottom witha throughput of 1 liter (or 5.6 BV) per hour. In order to execute theadsorption step, an aqueous stream with 20 grams per liter of thedipolar aprotic compound NMP dissolved in it and containing essentiallyno methanol was led through the column The concentration of NMP wasmeasured at the exit of the column. At the beginning of the adsorptionstep and during 50 minutes—or 4.7 BV—thereafter, the said concentrationwas zero, i.e. all of the NMP was adsorbed at the porous adsorbent. Thisestablished that the adsorption step was being done successfully. In thetimeframe between 50 and 70 minutes, the concentration of NMP graduallyincreased to 20 grams per liter; this so-called breakthrough curveestablished that full saturation of the porous adsorbent had taken placeand all NMP now passed through.

After the adsorbent had adsorbed the dipolar aprotic compound to themaximum extent, as determined via the breakthrough measurements, thereplacement step a1) was done by changing the in-flow to de-ionisedwater. One bed-volume of de-ionised water was used; this ensured thatany compounds not soluble in the desorbing agent were essentiallyremoved. During this time the NMP concentration at the exit remained atabout 20 grams per liter.

Subsequent to replacement step a1), the desorption step b) was executedby changing the in-flow of the column to methanol. 1.4 BV of methanolwas used. The NMP was found to be readily desorbed from the porousadsorbent by the methanol, evidenced by a sharp increase of the NMPconcentration at the exit to 130 grams per liter, then followed by adecline; the so-formed recovery solution was collected at the exit ofthe column and kept separate. The NMP concentration in the recoverysolution was found to be 75 g/liter.

After completion of the desorption step b), the regeneration step c) wasexecuted by changing the in-flow of the column to deionised water. About2.5 BV of deionised water was used, so as to remove the methanol fromthe porous adsorbent. During this time, the NMP concentration at theexit decreased to essentially zero. The column was thus regenerated andready for execution of step a) of a renewed cycle.

EXAMPLE 10

In order to execute adsorption step a) in combination with replacementstep a1), desorption step b) with methanol as desorbing agent,regeneration step c), and recovery step d), the following pilot-plantwork was done.

A stainless steel column was filled with porous adsorbent Lewatit® VP OC1163; the adsorbent was kept as a fixed-bed. The column was somewhatmore than 2000 mm long with an inner diameter of 109.1 mm; the inner bedvolume (BV) was 18.7 liter. The column was placed vertically; theliquids flowed from top to bottom with a throughput of 93.5 liter (or 5BV) per hour during the adsorption step a) and with a throughput of 46.7liter (or 2.5 BV) per hour in all other steps.

In order to execute the adsorption step, 10 BV of an aqueous mixture wasfed to the column The aqueous mixture was formed in a process for thepreparation of the C₁₄-aldehyde2-methyl-4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-2-butenal and had thefollowing composition: water 92.3 wt. %, NMP 1.2 wt. %, electrolytes(salts) 5.5 wt. %, NaOH 0.7 wt. %, rest impurities 0.3 wt. %. It wasfound typically that breakthrough began after 7-7.5 BV and was fullafter 9-9.5 BV.

Replacement step a1) was executed by changing the feed to deionisedwater and feeding 1 BV.

Subsequent to replacement step a1), the desorption step b) was executedby changing the in-flow of the column to methanol. 1.5 BV of methanolwas used. The so-formed recovery solution was collected at the exit ofthe column and kept separate. The NMP concentration in the recoverysolution was found to be 8.5 wt. %.

After completion of the desorption step b), the regeneration step c) wasexecuted by changing the in-flow of the column to deionised water. 2 BVof deionised water was used, so as to remove the methanol from theporous adsorbent. During this time, the NMP concentration at the exitdecreased to essentially zero, indicating that all of the NMP had leftthe column The column was thus regenerated and ready for execution ofstep a) of a renewed cycle.

The recovery solution was, in order to execute recovery step d), fed toa distillation column The top product consisted of 89.2 wt. % methanol,10.8 wt. % water and essentially no NMP. The bottom product consisted of0.1 wt. % water, 80.4 wt. % NMP and 18.5 wt. % of various impuritiesresulting from the preparation of the C₁₄ aldehyde. The bottom productwas fed to a thin-film evaporator; the top product consisted of NMP withabout 2 wt. % of impurities. This product could be re-used successfullyfor the process of preparation of the C₁₄-aldehyde.

The invention claimed is:
 1. A process for the preparation of2-methyl-4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-2-butenal (MTCB) whichcomprises: (1) providing an aqueous mixture comprised of MTCB and adipolar aprotic compound which is selected from the group consisting ofhexamethylphosphorous triamide (HMPT), 1-methyl-2-pyrrolidone (NMP),1-ethyl-2-pyrrolidone (NEP) and urea derivatives of the followingformula:

wherein R₁, R₂, R₃ and R₄ may each independently be H or a C₁-C₄ alkylgroup and wherein R₂ and R₃ may be part of a heterocyclic group, and (2)separating MTCB product from the aqueous mixture to form a productstream comprising the MTCB and an aqueous waste stream comprising thedipolar aprotic compound; and (3) treating the aqueous waste streamcomprising the dipolar aprotic compound to remove the dipolar aproticcompound therefrom by: a) an adsorption step which comprises bringingthe aqueous waste stream into contact with a porous adsorbent, whereinthe porous adsorbent is chosen such that the dipolar aprotic compoundadsorbs more readily to the porous adsorbent than water; and b) adesorption step which comprises bringing the porous adsorbent intocontact with a desorbing agent which comprises methanol to thereby forma recovery solution comprising the desorbing agent and the dipolaraprotic compound.
 2. A process for the preparation of2-methyl-4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-2-butenal (MTCB) whichcomprises: (1) providing an aqueous mixture comprised of MTCB and adipolar aprotic compound which is selected from the group consisting ofhexamethylphosphorous triamide (HMPT), 1-methyl-2-pyrrolidone (NMP),1-ethyl-2-pyrrolidone (NEP) and urea derivatives of the followingformula:

wherein R₁, R₂, R₃ and R₄ may each independently be H or a C₁-C₄ alkylgroup and wherein R₂ and R₃ may be part of a heterocyclic group, and (2)separating MTCB product from the aqueous mixture to form a productstream comprising the MTCB and an aqueous waste stream comprising thedipolar aprotic compound; and (3) treating the aqueous waste streamcomprising the dipolar aprotic compound to remove the dipolar aproticcompound therefrom by: a) an adsorption step which comprises bringingthe aqueous waste stream into contact with a porous adsorbent, whereinthe porous adsorbent is chosen such that the dipolar aprotic compoundadsorbs more readily to the porous adsorbent than water; b) areplacement step which comprises bringing the porous adsorbent intocontact with a replacement solution, said replacement solution being anaqueous solution containing at most 5 wt. % of electrolytes based on thetotal weight of the replacement solution and at most 20 wt. % of acompound or compounds that can act as desorbing agent; and c) adesorption step which comprises bringing the porous adsorbent intocontact with a desorbing agent which comprises methanol to thereby forma recovery solution comprising the desorbing agent and the dipolaraprotic compound.
 3. A process for the preparation of2-methyl-4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-2-butenal (MTCB) whichcomprises: (1) providing an aqueous mixture comprised of MTCB and adipolar aprotic compound which is selected from the group consisting ofhexamethylphosphorous triamide (HMPT), 1-methyl-2-pyrrolidone (NMP),1-ethyl-2-pyrrolidone (NEP) and urea derivatives of the followingformula:

wherein R₁, R₂, R₃ and R₄ may each independently be H or a C₁-C₄ alkylgroup and wherein R₂ and R₃ may be part of a heterocyclic group, and (2)separating MTCB product from the aqueous mixture to form a productstream comprising the MTCB and an aqueous waste stream comprising thedipolar aprotic compound; and (3) treating the aqueous waste streamcomprising the dipolar aprotic compound to remove the dipolar aproticcompound therefrom by: a) an adsorption step which comprises bringingthe aqueous waste stream into contact with a porous adsorbent, whereinthe porous adsorbent is chosen such that the dipolar aprotic compoundadsorbs more readily to the porous adsorbent than water; and b) adesorption step which comprises bringing the porous adsorbent intocontact with a desorbing agent which comprises methanol to thereby forma recovery solution comprising the desorbing agent and the dipolaraprotic compound; and c) a regeneration step which comprises bringingthe porous adsorbent into contact with a regeneration solution, saidregeneration solution being an aqueous solution containing at most 5 wt.% of electrolytes based on the total weight of the replacement solutionand at most 20 wt. % of a compound or compounds that can act asdesorbing agent, whereby the recovery solution is at least partlyseparated from the porous adsorbent.
 4. A process for the preparation of2-methyl-4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-2-butenal (MTCB) whichcomprises: (1) providing an aqueous mixture comprised of MTCB and adipolar aprotic compound which is selected from the group consisting ofhexamethylphosphorous triamide (HMPT), 1-methyl-2-pyrrolidone (NMP),1-ethyl-2-pyrrolidone (NEP) and urea derivatives of the followingformula:

wherein R₁, R₂, R₃ and R₄ may each independently be H or a C₁-C₄ alkylgroup and wherein R₂ and R₃ may be part of a heterocyclic group, and (2)separating MTCB product from the aqueous mixture to form a productstream comprising the MTCB and an aqueous waste stream comprising thedipolar aprotic compound; and (3) treating the aqueous waste streamcomprising the dipolar aprotic compound to remove the dipolar aproticcompound therefrom by: a) an adsorption step which comprises bringingthe aqueous waste stream into contact with a porous adsorbent, whereinthe porous adsorbent is chosen such that the dipolar aprotic compoundadsorbs more readily to the porous adsorbent than water; and b) adesorption step which comprises bringing the porous adsorbent intocontact with a desorbing agent which comprises methanol to thereby forma recovery solution comprising the desorbing agent and the dipolaraprotic compound, and (4) isolating the dipolar aprotic compound fromthe recovery solution.
 5. The process according to any one of claims1-4, wherein the porous adsorbent comprises a cross-linked resin.
 6. Theprocess according to claim 5, wherein the porous adsorbent has aspecific surface area of at least 400 m²/g.
 7. The process according toclaim 5, wherein the porous adsorbent comprises a cross-linkedpolystyrene-divinylbenzene resin.
 8. The process according to claim 4,which further comprises recycling the dipolar aprotic compound to step(1) for the formation of MTCB.
 9. The process according to any one ofclaims 1-3, which further comprises isolating the dipolar aproticcompound from the recovery solution, and recycling the dipolar aproticcompound to step (1) for the formation of MTCB.
 10. A method for thepreparation of vitamin A, which method comprises a process according toany one of claims 1-3.
 11. The process according to claim 10, whichfurther comprises isolating the dipolar aprotic compound from therecovery solution, and recycling the dipolar aprotic compound to step(1) for the formation of MTCB.
 12. A method for the preparation ofvitamin A, which method comprises a process according to claim
 4. 13.The process according to claim 12, which further comprises recycling thedipolar aprotic compound to step (1) for the formation of MTCB.